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CN107925098A - Fuel cell photocurable, fuel cell and encapsulating method - Google Patents

Fuel cell photocurable, fuel cell and encapsulating method Download PDF

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Publication number
CN107925098A
CN107925098A CN201680048479.3A CN201680048479A CN107925098A CN 107925098 A CN107925098 A CN 107925098A CN 201680048479 A CN201680048479 A CN 201680048479A CN 107925098 A CN107925098 A CN 107925098A
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CN
China
Prior art keywords
fuel cell
flange
photocurable
ester
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201680048479.3A
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Chinese (zh)
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CN107925098B (en
Inventor
曾我哲德
穴井麻央
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ThreeBond Co Ltd
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ThreeBond Co Ltd
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Publication of CN107925098A publication Critical patent/CN107925098A/en
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Publication of CN107925098B publication Critical patent/CN107925098B/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0284—Organic resins; Organic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C08F10/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
    • C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/042—Polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9008—Organic or organo-metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0286—Processes for forming seals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02B90/10—Applications of fuel cells in buildings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Sealing Material Composition (AREA)
  • Fuel Cell (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Fuel cell photocurable it is an object of the invention to provide the irradiation by ultraviolet isoreactivity energy-ray promptly to cure, excellent to the dielectric film as the difficult material being bonded, the bonding force of PP, PEN.Specifically, there is provided fuel cell photocurable, it is characterised in that contain following (A)~(C) components.(A) component：Intramolecular with more than 1 it is (methyl) acryloyl group, with including [CH2C(CH3)2] unit polyisobutene skeleton polymer；(B) component：Optical free radical polymerization initiator；(C) component：Methacrylate monomers.

Description

Fuel cell photocurable, fuel cell and encapsulating method
Technical field
The present invention relates to the irradiation by ultraviolet isoreactivity energy-ray promptly to cure, to the material as hardly possible bonding The excellent fuel cell photocurable of the dielectric film of matter, the bonding force of PP, PEN.
Background technology
In recent years, fuel cell receives much concern as automobile, home-use new energy resource system.Fuel cell is by making Hydrogen is chemically reacted with oxygen and takes the power generator of electricity.In addition, fuel cell is since energy efficiency when generating electricity is high, passes through hydrogen Reaction with oxygen and generate water, therefore be clean power generator of new generation.Fuel cell have polymer electrolyte fuel cell, This 4 modes of phosphoric acid type fuel cell, fused carbonate type fuel cell, solid oxide fuel cell, wherein, solid is high Molecule-type fuel cell due to operating temperature be compared with low temperature (80 DEG C or so) and be high generation efficiency, in automobile using power The electronic equipments such as source, home-use power generator, mobile phone are with enjoying expectation in the purposes such as Miniature Power Unit, emergency power supply.
As shown in Figure 1, the battery 1 of polymer electrolyte fuel cell be possess electrolyte film-electrode joint 5 (MEA), Support the structure of the separator 2 of the frame 6 of above-mentioned MEA and the flow path formed with gas, above-mentioned electrolyte film-electrode joint 5 The structure between air electrode 3a, fuel electrode 3b is held in polyelectrolyte membrane 4.
In order to start polymer electrolyte fuel cell, it is necessary to supply the fuel containing hydrogen to anode electrode with being individually insulated Gas, supply containing aerobic oxidizing gas cathode electrode.This is because if isolation is insufficient and gas and another gas Body mixes, it is likely that causes the decline of generating efficiency.From such background, for preventing fuel gas, oxygen etc. The purpose of leakage, mostly using sealant.Specifically, between adjacent separator, between separator and frame, frame Sealant is used between frame and dielectric film or MEA etc..
As the sealant used in polymer electrolyte fuel cell, due to be resistance to gas-premeable, it is low-moisture permeability, resistance to Hot, acid resistance, flexible excellent rubber elastomer, therefore, have studied the carry out silane using polyisobutene based polymer The hot curing resin composition (with reference to patent document 1) of alkylation reaction, use the carry out hydrosilylation of perfluoroalkyl polyether compound The hot curing resin composition (with reference to patent document 2) of reaction, the heat for carrying out hydrosilylation reactions using fluoropolymer Hardening resin composition (with reference to patent document 3), the hot curing resin composition (ginseng using Ethylene-Propylene-Diene rubber According to patent document 4).However, the hot curing resin composition of patent document 1~4 needs heating process to cure, because This, exists and spends activity time and worry because the deterioration of the dielectric film caused by heating is such the problem of.
Therefore, it is possible to realize that process shortens, prevents the light-cured resin combination of the deterioration of dielectric film caused by heat Thing receives much concern.Patent document 5,6 is disclosed containing polyisobutene diacrylate, (methyl) acrylic monomers, photoinitiator Photocurable.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2004-111146 publications
Patent document 2：Japanese Unexamined Patent Publication 2004-075824 publications
Patent document 3：Japanese Unexamined Patent Publication 2007-100099 publications
Patent document 4：Japanese Unexamined Patent Publication 2011-124258 publications
Patent document 5：Japanese Unexamined Patent Application Publication 2009-531516 publications
Patent document 6：Japanese Unexamined Patent Publication 2-88614 publications
The content of the invention
However, leakproofness in order to obtain, the Photocurable resin composition disclosed in patent document 5,6 is with polyisobutene two Acrylate is principal component, but photo-curable is insufficient.Further, since the polarity of polyisobutene diacrylate it is low and exist pair The problem of cementability difference of various components is such.In addition, the representative material of the polyelectrolyte membrane, frame as fuel cell PP (polypropylene), PEN (polyethylene naphthalate) difficult adhesive member of matter, the light-cured resin of patent document 5,6 Composition is more difficult to be bonded.
By above-mentioned reason, seek to have both by the irradiation of ultraviolet isoreactivity energy-ray promptly to cure and to making The fuel cell photocurable of the dielectric film of the material of difficult bonding, the bonding force of PP, PEN.
The present invention is in view of above-mentioned condition and completes, and is penetrated its purpose is to provide one kind by ultraviolet isoreactivity energy The irradiation of line and promptly cure, the excellent fuel cell of dielectric film, PP, PEN closing force to the material as hardly possible bonding Use photocurable.
The present invention is a kind of fuel cell photocurable, it is characterised in that containing following (A)~(C) into Point.
(A) component：In the molecule with more than 1 it is (methyl) acryloyl group, with including-[CH2C(CH3)2]-mono- The polyisobutylene polymer of the polyisobutene skeleton of member,
(B) component：Optical free radical polymerization initiator,
(C) component：Methacrylate monomers.
In addition, the other modes of the present invention can be as described below.
〔1〕
A kind of fuel cell photocurable, it is characterised in that contain following (A)~(C) components.
(A) component：In the molecule with more than 1 it is (methyl) acryloyl group, with including-[CH2C(CH3)2]-mono- The polyisobutylene polymer of the polyisobutene skeleton of member,
(B) component：Optical free radical polymerization initiator,
(C) component：Methacrylate monomers.
〔2〕
According to the fuel cell photocurable described in above-mentioned (1), wherein, (C) component is former with carbon The methacrylate monomers of the alkyl of subnumber 5~30 or with carbon number 5~30 ester ring type group methacrylic acid Ester monomer.
〔3〕
According to the fuel cell photocurable described in above-mentioned (2), wherein, (C) component is former with carbon The methacrylate monomers of the alkyl of subnumber 5~30, the methacrylate monomers should with alkyl are selected from metering system Heptyl heptylate, methacrylic acid -2- ethylhexyls, 2-Propenoic acid, 2-methyl-, octyl ester, isooctyl methacrylate, decyl-octyl methacrylate, Lauryl methacrylate, isodecyl methacrylate, lauryl methacrylate, methacrylic acid n-octadecane base Ester, methacrylic acid isooctadecane base ester, methacrylic acid nonadecane base ester, 3- heptyl decyl -1- methacrylates, methyl More than a kind in stearyl acrylate base ester, alternatively,
(C) component is the methacrylate monomers of the ester ring type group with carbon number 5~30, should have fat The methacrylate monomers of ring type group are selected from cyclohexyl methacrylate, methacrylic acid -4- butylcyclohexyls ester, methyl Acrylic acid bicyclopentyl ester, methacrylic acid dicyclopentenyl base ester, methacrylic acid dicyclopentenyl epoxide ester, methacrylic acid Isobornyl thiocyanoacetate, adamantylmethacrylate, dicyclopentenyl dimethylacrylate, Tricyclodecane Dimethanol dimethyl propylene More than a kind in olefin(e) acid ester.
〔4〕
According to the fuel cell photocurable any one of above-mentioned (1)~(3), wherein, (C) into The use level divided is to contain 3~300 mass parts relative to (A) component described in 100 mass parts.
〔5〕
According to the fuel cell photocurable any one of above-mentioned (1)~(4), wherein, (A) into It is divided into the polyisobutylene polymer represented by general formula (1).
(R1Represent monovalence or multivalence aromatic hydrocarbyl or monovalence or multivalence aliphatic alkyl, PIB is represented comprising-[CH2C (CH3)2The polyisobutene skeleton of]-unit, R4Represent the alkyl of the divalent that can include oxygen atom of carbon number 2~6. R2And R3Independently of one another represent hydrogen atom, carbon number 1~20 1 valency alkyl, R5Represent hydrogen atom, methyl, ethyl or third Base, n are any integer in 1~6.)
〔6〕
According to the fuel cell photocurable any one of above-mentioned (1)~(5), wherein, the fuel Battery by the use of photocurable be the separator as the component in fuel cell, frame, electrolyte, fuel electrode, air The sealant on the either member periphery in electrode and electrolyte film-electrode joint.
〔7〕
According to the fuel cell photocurable any one of above-mentioned (1)~(5), wherein, the fuel Battery with photocurable be sealant between the adjacent separator in fuel cell, in fuel cell every Between the frame and dielectric film or electrolyte film-electrode joint of sealant or fuel cell between off member and frame Sealant.
〔8〕
According to the fuel cell photocurable described in above-mentioned (6) or (7), wherein, the fuel cell is solid Body high molecular fuel battery.
〔9〕
A kind of solidfied material, is to carry out the fuel cell any one of (1)~(5) with photocurable What photocuring formed.
〔10〕
A kind of fuel cell, is comprising the seal between the adjacent separator in fuel cell, fuel cell In separator and frame between seal and fuel cell frame and dielectric film or electrolyte film-electrode joint Between seal in the fuel cell of any one, any one described seal include above-mentioned (9) described in solidfied material.
〔11〕
According to the fuel cell described in above-mentioned (10), wherein, the fuel cell is polymer electrolyte fuel cell.
〔12〕
A kind of encapsulating method, it is characterised in that be that at least two by containment member with least two flange is convex The method that at least a portion between edge is sealed, at least one in the flange are transmissive to active energy beam Light, the encapsulating method include following process：Appoint at least one surface coating above-mentioned (1)~(5) in the flange The process of fuel cell photocurable described in one；It is coated with one of the Photocurable resin composition The process that flange is bonded with another flange via the fuel cell with photocurable；And by it is described can be saturating Penetrating the flange irradiation active energy beam of light makes the fuel cell photo-curable sealant cures, and described at least two is convex The process that at least a portion between edge is sealed.
〔13〕
A kind of encapsulating method, it is characterised in that be that at least two by containment member with least two flange is convex The method that at least a portion between edge is sealed, including following process：At least one flange coating in the flange The process of fuel cell photocurable any one of above-mentioned (1)~(5)；To the fuel cell of the coating Make the fuel cell photo-curable sealant cures with photocurable irradiation active energy beam, formed by described The process for the gasket that the solidfied material of Photocurable resin composition is formed；By the configuration of another flange on the gasket, it will apply The flange and another described flange for being furnished with Photocurable resin composition are crimped via the gasket, by described in extremely The process that at least a portion between few 2 flanges is sealed.
〔14〕
A kind of encapsulating method, it is characterised in that be that at least two by containment member with least two flange is convex The method that at least a portion between edge is sealed, including following process：Match somebody with somebody at least one flange in the flange The process for putting gasket shape die for forming；To the gap between the gasket shape die for forming and the flange for being configured with the mould extremely The process of fuel cell photocurable any one of few part injection above-mentioned (1)~(5)；To the combustion Material battery photocurable, which irradiates the active energy beam, makes the fuel cell photo-curable sealant cures, The process for forming the gasket being made of the fuel cell with the solidfied material of photocurable；By the mould from described one The process that a flange is removed；By the configuration of another flange on the gasket, by one flange and another described flange Crimped via the gasket, the process that at least a portion between at least two flange is sealed.
The present invention is completes in view of the above circumstances, there is provided by the irradiation of ultraviolet isoreactivity energy-ray and fast Cure fastly, the fuel cell photo-curable excellent to the dielectric film as the difficult material being bonded, the bonding force of PP, PEN Sealant.
Brief description of the drawings
Fig. 1 is the schematic section of the monocell of fuel cell.
Fig. 2 is the schematic diagram for representing fuel cell entirety.
Embodiment
The detailed content of invention is illustrated below.
＜ (A) components ＞
(A) that is used in the present invention as long as component in the molecule with more than 1 (methyl) acryloyl group, with bag Containing-[CH2C(CH3)2The polyisobutylene polymer of the polyisobutene skeleton of]-unit is just not particularly limited.As (A) component, Such as long as there is-[CH2C(CH3)2]-unit (polyisobutene skeleton), or include "-[CH2C(CH3)2]-mono- The polyisobutylene polymer of other Component units beyond member ".(A) component suitably contains example relative to Component units total amount As more than 70 mass %, preferably comprise more than 75 mass %, further preferably more than 80 mass %-[CH2C(CH3)2]-mono- Member.In addition, (A) component suitably containing for example below 100 mass %-[CH2C(CH3)2]-unit, contains in other manner Have below 95 mass %, in addition, containing below 90 mass % in other manner.(A) component suitably preferably have 1~6, More preferably with 2~4, further preferably with 2~3, particularly preferably with 2 (methyl) acryloyl groups.It should illustrate that In the present invention, polymer is not only restricted to theory, such as can be defined as referring to repetition list of the main chain in polymer with monomer The structure of member and the compound being made of the repetitive unit of more than 100.
As above-mentioned (A) component, from photo-curable and to the closing force of dielectric film it is excellent from the viewpoint of, preferably by leading to The polymer with polyisobutene skeleton that formula (1) represents.As the concrete example of (A) component, can enumerate has (methyl) propylene The polyisobutylene polymer of acrylatoalkoxysilanes phenyl.In addition, the main framing of (A) component in the present invention is polyisobutene bone Frame, but in addition to the main monomer for using isobutene as the composition polyisobutene skeleton, as long as do not damage the present invention's The scope of effect, then can also be copolymerized other monomers.In addition, from the aspect of operability is excellent, (A) component is preferably normal It is liquid under warm (25 DEG C).
In formula (1), R1Represent monovalence or multivalence aromatic hydrocarbyl or monovalence or multivalence aliphatic alkyl, be preferably more Valency aromatic hydrocarbyl, particularly preferably phenylene.PIB represents above-mentioned comprising-[CH2C(CH3)2]-unit (or by-[CH2C (CH3)2]-unit is formed) include-[CH2C(CH3)2The polyisobutene skeleton of]-unit.R4Expression can include the carbon of oxygen atom The divalent alkyl of atomicity 2~6, is preferably the alkyl of carbon number 2 or 3.R2And R3Hydrogen atom, carbon atom are represented independently of one another 1 valency alkyl of number 1~20, is preferably hydrogen atom.R5Represent hydrogen atom, methyl, ethyl, be preferably hydrogen atom, methyl.N for 1~ Any integer in 6, particularly preferred 2~4 integer.
The molecular weight of (A) component in the present invention is not particularly limited, and is examined from physical property after mobility, curing etc. To consider, number-average molecular weight is for example preferably 500~500000, is more preferably 1000~100000, particularly preferably 3000~ 50000.It should illustrate that above-mentioned number-average molecular weight is converted by using the polystyrene standard of size exclusion chromatography (SEC) Method calculates.
(A) component in the present invention is not particularly limited in 25 DEG C of viscosity, considers from operability etc., such as preferably For 5~3000Pas, more preferably 50~2500Pas, particularly preferably 100~2000Pas.In addition, the viscosity is for example It is preferably more than 50Pas for more than 5Pas, more preferably more than 100Pas, is, for example, below 3000Pas, preferably For below 2500Pas, more preferably below 2000Pas.Particularly preferred viscosity is 1550Pas.It should illustrate that as long as There is no specified otherwise, then the measure of viscosity determines the viscosity at 25 DEG C using cone plate type viscometer.
(A) component in the present invention is not particularly limited in 25 DEG C of viscosity, considers from operability etc., such as preferably For 5~3000Pas, more preferably 50~2500Pas, particularly preferably 100~2000Pas.In addition, the viscosity is for example It is preferably more than 50Pas for more than 5Pas, more preferably more than 100Pas, is, for example, below 3000Pas, preferably For below 2500Pas, more preferably below 2000Pas.Particularly preferred viscosity is 1550Pas.It should illustrate that as long as There is no specified otherwise, then the measure of viscosity determines the viscosity at 25 DEG C using cone plate type viscometer.
As the manufacture method of above-mentioned (A) component, it is not particularly limited, known method can be used.For example, it can enumerate In Polymer Bulletin, volume 6, page 135~141 (1981), T.P.Liao and J.P.Kennedy and Polyer Bulletin, volume 20, page 253~260 (1988), polymerize terminal hydroxyl polyisobutene disclosed in Puskas et al. Thing and method etc. obtained from acryloyl chloride or methacrylic chloride reaction.
In addition, the manufacture method as other (A) components, can enumerate makes terminal hydroxyl polyisobutylene polymer with having Method obtained from the reaction of the compound of (methyl) acryloyl group and isocyanate group；Make terminal hydroxyl polyisobutylene polymer, Compound with isocyanate group and method obtained from being reacted with the compound of (methyl) acryloyl group and hydroxyl；Make Terminal hydroxyl polyisobutylene polymer is handed over (methyl) acrylic acid or (methyl) acrylic acid lower ester by dehydration esterification method or ester Method etc. obtained from changing method reaction.
In addition, the manufacture method as the above-mentioned polyisobutylene polymer represented by general formula (1), is not particularly limited, it is excellent Choosing can enumerate disclosed in Japanese Unexamined Patent Publication 2013-216782 publications by make halogen end thereof polyisobutylene polymer with such as by leading to What formula (2) represented has method obtained from the reaction of the compound of (methyl) acryloyl group and phenoxy group.In addition, above-mentioned halogen end End polyisobutylene polymer can be obtained by known method, such as can be obtained by cationic polymerization, more preferably logical Cross living cationic polymerization and obtain.
In formula (2), R2、R3、R4And R5It can be the definition as above stated in formula (1).Specifically, R4Represent carbon number 2 The alkyl of~6 divalent comprising oxygen atom.R2And R3Independently of one another represent hydrogen atom, carbon number 1~20 1 valency hydrocarbon Base.R5Represent hydrogen atom, methyl, ethyl.As the compound represented by above-mentioned formula (2), such as acrylic acid phenoxy group can be enumerated Methyl esters, acrylate, acrylic acid phenoxy-propyl etc., are preferably acrylate.
＜ (B) components ＞
It is used in the present invention as (B) as long as the optical free radical polymerization initiator of component is penetrated by irradiating active-energy Line and generating makes the compound of the cured free radical of (A) component of the present invention etc. just not limit.Here, active energy beam bag Containing the ultraviolet of the electromagnetic waves such as the radioactive ray such as alpha ray or β rays, gamma-rays or X-ray, electron beam (EB), 100~400nm or so Sensu lato all light such as the luminous ray of line, 400~800nm or so, are preferably ultraviolet.As (B) component, such as can lift Go out acetophenone system optical free radical polymerization initiator, benzoin system optical free radical polymerization initiator, benzophenone series optical free radical to gather Close initiator, thioxanthones system optical free radical polymerization initiator, acylphosphine oxide system optical free radical polymerization initiator, titanocenes system Optical free radical polymerization initiator etc., wherein, obtain the sight of excellent curability solidfied material from by irradiating active energy beam Point sets out, and is preferably acetophenone system optical free radical polymerization initiator, benzophenone series optical free radical polymerization initiator, acylphosphanes oxygen Compound system optical free radical polymerization initiator.In addition, these can be used alone, and two or more can also be used.
As above-mentioned acetophenone system optical free radical polymerization initiator, it is not particularly limited, such as diethoxybenzene can be enumerated Ethyl ketone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, benzyl dimethyl ketal, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyls Base -2- propyl group) ketone, 1- hydroxy-cyclohexyl-phenyls -one, 2- methyl -2- morpholino (4- thiomethylphenyls) propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls) butane, 2- hydroxy-2-methyls -1- [4- (1- methyl ethylenes) benzene Base] acetone oligomer etc., but it's not limited to that., can as the commercially available product of above-mentioned acetophenone system optical free radical polymerization initiator Enumerate IRGACURE184, IRGACUR1173, IRGACURE2959, IRGACURE127 (BASF societies system), ESACURE KIP- 150 (Lamberti s.p.a. societies systems).
As above-mentioned benzophenone series optical free radical polymerization initiator, such as benzophenone, 4,4 '-dichloro can be enumerated Ketone, dihydroxy benaophenonel, 2 methyl benzophenone, 2- ethylbenzophenones, 3- methyl benzophenones, 3- ethyl hexichol first Ketone, 4- methyl benzophenones, 4- ethylbenzophenones, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone and by this Inductor of a little molecular weights etc..
As above-mentioned acylphosphine oxide system optical free radical polymerization initiator, be not particularly limited, for example, can enumerate it is double (2, 4,6- trimethylbenzoyls)-phenyl-phosphine oxide, 2,4,6- trimethylbenzoyl-diphenyls-phosphine oxide etc., but be not limited to This.As the commercially available product of above-mentioned acylphosphine oxide system optical free radical polymerization initiator, can enumerate IRGACURE TPO, IRGACURE819, IRGACURE819DW (BASF societies system).
The use level of (B) component of the present invention is not particularly limited, relative to above-mentioned (A) component of 100 mass parts, from light It is preferably 0.1~30 mass parts from the viewpoint of curability, more preferably 0.5~20 mass parts, particularly preferably 1~15 matter Measure part.
＜ (C) components ＞
Methacrylate monomers as (C) component of the present invention are the freedom produced using (B) component of the present invention The compound that base kind is polymerize, from various reactive diluents select the present invention (C) component, and by with the present invention It is other into subassembly and with to the excellent significant effect of the dielectric film of material as hardly possible bonding, the bonding force of PP, PEN Fruit.As (C) component, mix from (A) component with the present invention, and from the aspect of photo-curable is excellent, it is however preferred to have The methacrylate monomers of the alkyl of carbon number 5~30 or with carbon number 5~30 ester ring type group methyl-prop Olefin(e) acid ester monomer, the particularly preferably methacrylate monomers with above-mentioned ester ring type group.Herein, as above-mentioned carbon atom Number, is, for example, more than 2, is preferably more than 3, more preferably more than 5, more preferably more than 7, and is, for example, Less than 30, be preferably less than 20, more preferably less than 15, more preferably less than 10.These compounds can be each From exclusive use, two or more uses can also be mixed.But (C) component excludes (A) component of the present invention.
As the methacrylate monomers of the above-mentioned alkyl with carbon number 5~30, it is not particularly limited, such as Metering system heptyl heptylate, methacrylic acid -2- ethylhexyls, 2-Propenoic acid, 2-methyl-, octyl ester, isooctyl methacrylate, first can be enumerated Base decyl acrylate, lauryl methacrylate, isodecyl methacrylate, lauryl methacrylate, metering system Sour n-octadecane base ester, methacrylic acid isooctadecane base ester, methacrylic acid nonadecane base ester, 3- heptyl decyl -1- methyl Acrylate, stearyl methacrylate etc..In addition, as the ester ring type group with above-mentioned carbon number 5~30 Methacrylate monomers, can enumerate cyclohexyl methacrylate, methacrylic acid -4- butylcyclohexyls ester, methacrylic acid two Cyclopentyl ester, methacrylic acid dicyclopentenyl base ester, methacrylic acid dicyclopentenyl epoxide ester, methacrylic acid isoborneol Ester, adamantylmethacrylate, dicyclopentenyl dimethylacrylate, Tricyclodecane Dimethanol dimethylacrylate Deng (C) component can be used alone or be used as two or more mixtures.
As the commercially available product of the methacrylate monomers of the alkyl with above-mentioned carbon number 5~30, SMA can be enumerated (Mitsubishi Gas Chemical Co., Ltd's system), LMA, SMA, (BASF societies system), LIGHT ESTER EH, LIGHT ESTER ID, LIGHT ESTER L, LIGHT ESTER L-7, LIGHT ESTER S (Kyoeisha Chemical Co., Ltd.), S (Xin Zhong villages chemistry Industrial Co., Ltd's system), LMA, SMA, HMA (ARKEMA Co. Ltd. systems), LMA, SMA (Mitsubishi's Rayon Co. Ltd. systems), SR242, SR313, SR324, SR493D (Sartomer societies system) etc..In addition, as the alicyclic ring with above-mentioned carbon number 5~30 The commercially available product of the methacrylate monomers of formula group, can enumerating FA-512M, FA-512MT, FA-513M, (Hitachi is melted into strain formula Commercial firm's system), DCP (Xin Zhong villages chemical industry Co. Ltd. system), CHMA (BASF societies system), BX-ADMA, BX-DCPMA (BIMAX societies System), LIGHT ESTER IB-X (Kyoeisha Chemical Co., Ltd.), CHMA (Mitsubishi's Rayon Co. Ltd. systems), SR423 (Sartomer societies system) etc..
The use level for being somebody's turn to do (C) component is not particularly limited, and is preferably 3~300 matter relative to (A) component of 100 mass parts Measure part, more preferably 5~200 mass parts, particularly preferably 10~100 mass parts.In this case, (as long as C) component is 3 mass More than part, then surface cure need not be reduced, as long as 300 is below mass part, then need not reduce this photocurable The moisture permeability of solidfied material and it is preferred that.
＜ any conditions ＞
For the present invention sealant, in the range of the purpose of the present invention is not damaged, can use acrylate monomer, Oligomer ((A) component and (C) component that do not include the present invention), thermal free radical initiator with (methyl) acryloyl group, gather It is the various elastomers such as mercaptan compound, tertiary amine compound, styrene based copolymer, packing material, preserving stabilizer, anti-oxidant The additives such as agent, light stabilizer, plasticizer, pigment, fire retardant, closely sealed imparting agent and surfactant.
Aforesaid propylene acid ester monomer is not particularly limited, such as can enumerate ethyl acrylate, n-butyl acrylate, acrylic acid The tert-butyl ester, isobutyl acrylate, acrylic acid-2-ethyl caproite, isodecyl acrylate, butoxy diethylene glycol acrylate, first Epoxide polyethylene glycol acrylate, glycidyl acrylate, lauryl acrylate, stearyl acrylate base ester, tetrahydrofurfuryl third Olefin(e) acid ester, caprolactone modification tetrahydrofurfuryl acrylate, cyclohexyl acrylate, acrylic acid bicyclopentyl ester, acrylic acid bicyclic penta Alkenyl esters, acrylic acid double cyclopentenyl epoxide ester, isobornyl acrylate, acrylic acid adamantane esters, benzyl acrylate, propylene Acid phenenyl ester, acrylate, phenoxy group diethylene glycol acrylate, phenoxy group tetraethylene glycol acrylate, acrylic acid Nonylphenoxy ethyl ester, acrylate, butoxy ethyl, acrylic acid -2- hydroxyl ethyl esters, 2-hydroxypropyl acrylate, acrylic acid -4- hydroxyl fourths Ester, glycerol acrylate, acrylic acid trifluoro ethyl ester, γ-acryloxypropyl trimethoxy silane, acryloyl morpholine, propylene Sour morpholinoethyl ester, acrylate, acrylic acid diethylamino ethyl ester, acrylic acid N, N- dimethylamino Ethyl ester, acrylic acid N, N- dimethylaminopropyl ester, 3- acryloxypropyls trimethoxy silane, ethylene glycol diacrylate Ester, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1.6- hexane diol dipropyls Olefin(e) acid ester, 1.9- nonanes omega-diol diacrylate, glycerol diacrylate, neopentylglycol diacrylate, stearic acid modified season Penta tetrol diacrylate, dicyclopentenyl diacrylate, two acryloyl chlorinated isocyanurates, two propylene of alkylen oxide-modified bis-phenol Acid esters, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, three (acryloyl-oxyethyl) chlorinated isocyanurates, Two (trimethylolpropane) tetraacrylates, tetramethylol methane tetraacrylate, dipentaerythritol monohydroxypentaacryande, alkyl Modified Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate etc..These acrylate monomers can be used alone Or it can be used as two or more mixtures.
As the oligomer ((A) component and (C) component that do not include the present invention) with above-mentioned (methyl) acryloyl group, do not have It is particularly limited to, such as carbamate (methyl) acrylate, the hydrogenated butadiene polymer skeleton of polybutadiene skeleton can be enumerated Carbamate (methyl) acrylate, carbamate (methyl) acrylate of polycarbonate backbone, polyether skeleton Carbamate (methyl) acrylate, the amino of castor oil skeleton of carbamate (methyl) acrylate, polyester backbone Formic acid esters (methyl) acrylate, isoprene (methyl) acrylate, hydrogenated isoprene system (methyl) acrylate, ring Oxygen (methyl) acrylate, acrylate copolymer containing (methyl) acrylic etc., wherein, from (A) component with the present invention, (C) from the aspect of the intermiscibility of component is excellent, preferably carbamate (methyl) acrylate of polybutadiene skeleton, hydrogenation Carbamate (methyl) acrylate of polybutadiene skeleton, carbamate (methyl) acrylate of castor oil skeleton, Isoprene (methyl) acrylate, hydrogenated isoprene system (methyl) acrylate.
Above-mentioned thermal free radical initiator is not particularly limited, such as can enumerate ketone peroxide, ketal peroxide, dialkyl group mistake Oxide, hydrogen peroxide, peroxyester, diacyl peroxide, peroxy dicarbonate etc..These compounds can be each single Solely use, it is two or more alternatively, it is also possible to be used in mixed way.
As above-mentioned poly-thiol compound, it is not particularly limited, such as trimethylolpropane tris (3- mercaptopropionic acids can be enumerated Ester), pentaerythrite four (3-thiopropionate), trimethylolpropane tris (3- mercaptobutylates), trimethylolethane trimethacrylate (3- mercaptos Base butyrate), trimethylolethane trimethacrylate (3- mercaptobutylates), ethylene glycol double (3- thioglycolates), double (the 3- mercaptos of butanediol Base ethyl glycolate), trimethylolpropane tris (3- thioglycolates), pentaerythrite four (3- thioglycolates), three [(3- Mercaptopropionyl epoxide)-ethyl]-isocyanuric acid ester, pentaerythrite four (3-thiopropionate), double (the 3- mercaptopropionic acids of tetraethylene glycol Ester), dipentaerythritol six (3-thiopropionate), pentaerythrite four (3- mercaptobutylates), double (the 3- sulfydryl butyryl oxygen of 1,4- Base) butane, 1,3,5- tri- (3- sulfydryls butoxyethyl group) -1,3,5-triazines -2,4,6 (1H, 3H, 5H)-triketones etc., these chemical combination Thing can be used individually, two or more alternatively, it is also possible to be used in mixed way.
As the commercially available product of above-mentioned poly-thiol compound, for example, can enumerate TMTP, PETP (shallow lake Chemical Co., Ltd. system), TEMPIC, TMMP, PEMP, PEMP-II-20P, DPMP (SC organic chemistry Co. Ltd. system), MTNR1, MTBD1, MTPE1 are (clear With electrician's Co. Ltd. system) etc., but it is not limited to these.These compounds can be used individually, alternatively, it is also possible to mix Using two or more.
Tertiary amine compound can be coordinated to the present invention for the purpose for improving photo-curable.As tertiary amine compound, do not have It is particularly limited to, such as can enumerates trimethylamine, triethylamine, tri-n-butylamine, N, N '-diethanol amine, N, N '-dimethyl-para-totuidine, N, N '-dimethyl-aniline, N- metil-diethanolamines, N- methyl-dimethanolamine, N, N '-dimethyl amino-acetophenone, N, N '- Dimethylamino benzophenone, N, N '-diethylamino-benzophenone, triisopropanolamine etc..
Can for adjustment solidfied material rubber physical property purpose and to styrene based copolymer of the present invention.As benzene Vinyl copolymer, is not particularly limited, such as can enumerate styrene-butadiene copolymer, styrene-isoprene copolymer (SIP), styrene-butadiene copolymer (SB), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-isobutyl Alkene-styrol copolymer (SIBS), acrylonitritrile-styrene resin (AS), Acrylnitrile-Butadiene-Styrene (ABS) Deng.
It is steady preservation can not to be damaged to present invention addition for the purpose of elasticity modulus, the mobility for improveing solidfied material etc. The qualitatively packing material of degree.Specifically, organic matter powder, inanimate matter powder, metallic powder etc. can be enumerated.As nothing The packing material of machine matter powder, can enumerate glass, aerosil, aluminium oxide, mica, ceramics, organic silicon rubber powder, carbon Sour calcium, aluminium nitride, carbon dust, kaolin, dry clay mineral, dring silicon diatomaceous earth etc..The use level of inanimate matter powder is relative to (A) 100 mass parts of component are preferably 0.1~100 mass parts or so.More than 0.1 mass parts, then sufficient effect can be expected, It is below mass part if 100, then photocurable mobility can be fully kept, and certain operation can be kept Property, therefore preferably.
Aerosil can be for the viscosity or raising solidfied material for adjusting fuel cell photocurable The purpose of mechanical strength and coordinate.It is preferred that it can use with organochlorosilane class, polysiloxane, hexamethyldisilazane etc. Carry out aerosil that silicic acid anhydride forms etc..As the concrete example of aerosil, such as Japan can be enumerated Trade name Aerosil R974 of Aerosil, R972, R972V, R972CF, R805, R812, R812S, R816, R8200, The commercially available products such as RY200, RX200, RY200S, R202.
As the packing material of organic matter powder, such as polyethylene, polypropylene, nylon, cross-linked acrylic acid, crosslinking can be enumerated Polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral resin, makrolon.The use level of organic matter powder relative to (A) into It is preferably 0.1~100 mass parts or so to divide 100 mass parts.More than 0.1 mass parts, then sufficient effect can be expected, if It is below mass part for 100, then the mobility of photocurable can be fully kept, and operability can be kept, therefore It is preferred that.
As the packing material of metallic powder, for example, can enumerate gold, platinum, silver, copper, indium, palladium, nickel, aluminium oxide, tin, iron, Aluminium, stainless steel etc..The use level of metallic powder is preferably 0.1~100 mass parts or so relative to 100 mass parts of (A) component, More preferably 1~50 mass parts.
Preserving stabilizer can also be added to the present invention.As preserving stabilizer, can also add benzoquinones, hydroquinone, The free base absorbant such as hydroquinone monomethyl ether, ethylenediamine tetra-acetic acid or its 2- sodium salt, oxalic acid, acetylacetone,2,4-pentanedione, adjacent aminobenzene Metal-chelators such as phenol etc..
Antioxidant can also be added to the present invention.As antioxidant, such as beta-naphthoquinone, 2- methoxyl group -1 can be enumerated, 4- naphthoquinones, methyl hydroquinone, hydroquinone, hydroquinone monomethyl ether, single tert-butyl hydroquinone, 2,5- di-t-butyls pair The quinone based compounds such as benzenediol, 1,4-benzoquinone, 2,5- diphenyl -1,4-benzoquinone, 2,5- di-t-butyls -1,4-benzoquinone；Phenthazine, 2,2- are sub- Methyl-bis- (4- methyl-6-tert-butylphenols), catechol, tert-butyl catechol, 2- butyl -4-hydroxyanisol, 2,6- Di-t-butyl-paracresol, the 2- tert-butyl groups -6- (the 3- tert-butyl group -2- hydroxy-5-methyl bases benzyl) -4- aminomethyl phenyls acrylate, 2- (1- (2- hydroxyl -3,5- di-tert-pentyl-phenyls) ethyl) -4,6- di-tert-pentyl-phenyls acrylate, 4,4 '-butylidenebis (uncle 6- Butyl -3- methylphenols), 4,4 '-thiobis (the 6- tert-butyl group -3- methylphenols), the double (2- (3- (the 3- tert-butyl group -4- hydroxyls of 3,9- Base -5- aminomethyl phenyls) propionyloxy) -1,1- dimethyl ethyls) -2,4,8,10- four oxaspiro (5,5) hendecane, pentaerythrite Double (3- (3,5- di-t-butyl -4- the hydroxy benzenes of four (3- (3,5- di-tert-butyl-hydroxy phenyls) propionic esters), thiodiethylene Base) propionic ester), octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester, the double (3- of N, N '-hexane -1,6- diyl (3,5- di-tert-butyl-hydroxy phenyls) propionamide), benzenpropanoic acid, double (1,1- the dimethyl ethyls) -4- hydroxyls of 3,5-, C7-C9Side Alkane base ester, 2,4- dimethyl -6- (1- methyl pentadecyl) phenol, diethyl ((double (1,1- dimethyl ethyls) -4- of 3,5- Hydroxy phenyl) methyl) phosphonate ester, 3,3 ', 3 ", 5,5 ', 5 "-six tert-butyl group-a, a ', a "-(mesitylene -2,4,6- tolyls) Double ((double (1,1- the dimethyl ethyls) -4- hydroxy phenyls of 3,5-) methyl) the phosphonic acids calcium of three paracresol, diethyl, the double (octyl groups of 4,6- Sulfidomethyl) it is-o-cresol, ethylenebis (oxygen ethylidene) double (3- (a 5- tertiary butyl-4-hydroxies-tolyl) propionic esters), six sub- Methyl pair (3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) -1, 3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, 1,3,5- tri- ((the 4- tert-butyl group -3- hydroxyl -2,6- xylyls) methyl) -1, Reaction product, the 2,6- bis- of 3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, N- phenylanilines and 2,4,6- trimethylpentenes The phenols such as the tert-butyl group -4- (double (pungent the sulfenyl) -1,3,5- triazine -2- bases amino of 4,6-) phenol, picric acid, citric acid；Three (2,4- Di-tert-butyl-phenyl) phosphite ester, three (2- ((2,4,8,10- tetra-terts dibenzo (d, f) (1,3,2) dioxa phosphine -6- Base) epoxide) ethyl) amine, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, the double (double (1,1- bis- of 2,4- of phosphorous acid Methylethyl) -6- aminomethyl phenyls) ethyl ester, ' the double sub- phosphines of-diyl of four (2,4- di-tert-butyl-phenyls) (1,1- double phenyl) -4,4 Acid esters, 6- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propoxyl group) -2,4,8,10- tetra-terts dibenzo (d, f) (1, 3,2) phosphorus series compound such as dioxa phosphine；Dilauryl 3,3 '-thiodipropionate, myristyl 3,3 '-thio-2 acid Ester, distearyl 3,3 '-thiodipropionate, pentaerythrite base four (3- lauryl thiopropionates), 2-mercaptobenzimidazole Deng chalcogenide compound；The amine compounds such as phenthazine；Lactone based compound；Vitamin E based compound etc..Wherein, preferred phenol system Compound.
Light stabilizer can also be added to the present invention.As light stabilizer, for example, can enumerate it is double (2,2,6,6- tetramethyls- 4- piperidyls) sebacate, double (1,2,2,6,6- pentamethyl -4- piperidyls) sebacates, 4- benzoyloxys -2,2,6,6- Tetramethyl piperidine, 1- (2- (3- (3,5- di-tert-butyl-hydroxy phenyls) propionyloxy) ethyl) -4- (3- (bis- tertiary fourths of 3,5- Base -4- hydroxy phenyls) propionyloxy) -2,2,6,6- tetramethyl piperidines, 1,2,2,6,6- pentamethyls -4- piperidyls-metering system Acid esters, double (1,2,2,6,6- pentamethyl -4- piperidyls) ((double (1,1- the dimethyl ethyls) -4- hydroxy phenyls of 3,5-) methyl) fourth Phenyl malonic ester, decanedioic acid double (2,2,6,6- tetramethyls -1- (octyloxy) -4- piperidyls) ester, 1,1- dimethyl ethyl peroxides Change reaction product, the N, N ' of hydrogen and octane, N ", N " '-four (4,6- couples-(butyl-(N- methyl -2,2,6,6- tetramethyl piperazines Pyridine -4- bases) amino)-triazine -2- bases) -4,7- diaza decane -1,10- diamines, dibutyl amine 1,3,5- triazines N, N '-bis- (2,2,6,6- tetramethyl -4- piperidyl -1,6- hexamethylene diamines and N- (2,2,6,6- tetramethyl -4- piperidyls) butylamine Condensation polymer, it is poly- ((6- (1,1,3,3- tetramethyl butyls) amino -1,3,5- triazine -2,4- diyls) ((2,2,6,6- tetramethyls - 4- piperidyls) imino group) hexa-methylene ((2,2,6,6- tetramethyl -4- piperidyls) imino group)), dimethyl succinate and 4- hydroxyls The polymer of base -2,2,6,6- tetramethyl -1- piperidine ethanols, 2,2,4,4- tetramethyls -20- (β-lauryl Epoxide carbonyl) second Two spiral shell (51112) heneicosane -21- ketone of base -7- oxa- -3,20- diazas, Beta-alanine, N,-(2,2,6,6- tetra- Methyl -4- piperidyls)-dodecyl ester/tetradecane base ester, N- acetyl group -3- dodecyls -1- (2,2,6,6- tetramethyls -4- Piperidyl) pyrrolidine-2,5-dione, two spiral shell (5,1,11,2) of 2,2,4,4- tetramethyl -7- oxa- -3,20- diazas 21 Alkane -21- ketone, 2,2,4,4- tetramethyl -21- oxa- -3,20- diazabicylos-(5,1,11,2)-heneicosane -20- propionic acid ten Dialkyl ester/tetradecane base ester, malonic acid, ((4- methoxyphenyls)-methylene)-bis- (1,2,2,6,6- pentamethyl -4- piperidines Base) ester, the high-grade aliphatic ester of 2,2,6,6- tetramethyl -4- piperidine alcohols, 1,3- benzenedicarboxamides, N, N '-bis- (2,2,6,6- tetra- Methyl -4- piperidyls) etc. amine system of being obstructed；The benzophenone series such as 2-hydroxy-4-n-octoxybenzophenone (OctaBenzone) Compound；2- (2H- benzotriazole -2- bases) -4- (1,1,3,3- tetramethyl butyls) phenol, 2- (2- hydroxy-5-methyl bases phenyl) benzene And triazole, 2- (2- hydroxyls -3- (3,4,5,6- tetrahydric phthalimides-methyl) -5- aminomethyl phenyls) benzotriazole, 2- (the 3- tert-butyl group -2- hydroxy-5-methyl bases phenyl) -5- chlorobenzotriazoles, 2- (2- hydroxyl -3,5- di-tert-pentyl-phenyls) benzo three The reaction generation of azoles, methyl 3- (3- (2H- benzotriazole -2- bases) -5- tert-butyl-hydroxy phenyls) propionic esters and polyethylene glycol The benzotriazole based compounds such as thing, 2- (2H- benzotriazole -2- bases) -6- dodecyl -4- methylphenols；2,4- di-t-butyls The benzoic ether based compounds such as phenyl -3,5- di-tert-butyl-4-hydroxybenzoic acid esters；2- (4,6- diphenyl -1,3,5- triazines - 2- yls) the triazine based compound such as -5- ((hexyl) epoxide) phenol etc..Particularly preferably be obstructed amine compound.
Closely sealed imparting agent can also be added to the present invention.As closely sealed imparting agent, 3- methacryloxies third can be enumerated Ylmethyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silanes, 3- methacryloyloxypropyl methyls Diethoxy silane, 3- methacryloxypropyls, 3- acryloxypropyls trimethoxy silane, first Base acryloxy octyl group trimethoxy silane, vinyltrimethoxysilane, vinyl trichlorosilane, vinyl triethoxyl Silane, vinyl-three ('beta '-methoxy ethyoxyl) silane, γ-r-chloropropyl trimethoxyl silane, β-(3,4- epoxycyclohexyls) second Base trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ mercaptopropyitrimethoxy silane, gamma-amino Propyl-triethoxysilicane, N- β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, N- β-(amino-ethyl)-γ-ammonia Base hydroxypropyl methyl dimethoxysilane, γ-ureidopropyltriethoxysilane, hydroxyethyl methacrylate phosphate, methyl-prop Alkene trimethylammonium phosphate ester acid, half salt of methacryloxyethyl phosphate ester acid monoethylamine, methacrylic acid 2- Hydroxy methacrylate phosphate etc..Among these, preferably hydroxyethyl methacrylate phosphate, methacryloxyethyl acid phosphorus Acid esters, half salt of methacryloxyethyl phosphate ester acid monoethylamine, 2-hydroxyethyl methacrylate phosphate etc..It is close Close property imparting agent content relative to 100 mass parts of (A) component be preferably 0.05~30 mass parts, more preferably 0.2~ 10 mass parts.
The fuel cell of the present invention can be manufactured with photocurable by known method.For example, can be with Manufacture in the following way：Coordinate (A) component~(C) component of ormal weight and other any conditions, it is mixed using mixer etc. Attach together and put, temperature preferably at 10~70 DEG C, more preferably 20~50 DEG C, particularly preferably mixed under room temperature (25 DEG C) it is preferred 0.1~5 it is small when, more preferably 30 minutes~3 it is small when, manufacture within particularly preferred 60 minutes or so.
＜ coating methods ＞
As the method that the fuel cell of the present invention is coated on to adherend with photocurable, can use known Sealant, the method for bonding agent.It is, for example, possible to use utilize the dispensing of automatic coating machine, spraying, ink-jet, silk-screen printing, recessed The methods of version printing, dipping, spin coating.In addition, from the viewpoint of coating, fuel cell of the invention is sealed with photo-curable Agent is liquid preferably at 25 DEG C.
＜ curings ＞
Active energy beam as described above is irradiated by the photocurable of the fuel cell to the present invention, such as Light source during its curing is not particularly limited when light in ultraviolet, visible ray, for example, Cooper-Hewitt lamp, middle medium pressure mercury can be enumerated Lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, black light lamp, microwave-excitation mercury vapor lamp, metal halide lamp, sodium vapor lamp, halogen lamp, xenon Lamp, LED, fluorescent lamp, sunlight, electron beam illuminating device etc..From the viewpoint of the characteristic of solidfied material, the exposure of light irradiation Preferably accumulative light quantity 10kJ/m2More than, more preferably 15kJ/m2More than.
＜ solidfied materials ＞
The solidfied material of the present invention is ultraviolet by Photocurable resin composition irradiation of the above-mentioned curing to the present invention Line isoreactivity energy-ray makes what its curing formed.As long as the solidfied material of the present invention is the Photocurable resin composition of the present invention Cure the solidfied material formed, then its curing can be any means.
＜ purposes and sealant ＞
As the specific purposes of the sealant of the present invention, since the photocurable of the present invention or its solidfied material are Low gas-premeable, low-moisture permeability, heat resistance, acid resistance, flexible excellent rubber elastomer, therefore, can enumerate fuel cell, Solar cell, dye-sensitized solar cell, lithium ion battery, electrolytic capacitor, liquid crystal display, organic EL are shown Device, Electronic Paper, LED, hard disk unit, photodiode, optical communication circuit, electric wire Cable fiber, optoisolator, IC card Deng layered product, sensor, substrate, medical medical device equipment etc..In these purposes, photo-curable of the invention sealing Agent promptly cures due to the irradiation by ultraviolet isoreactivity energy-ray, to the dielectric film of the material as hardly possible bonding Closing force it is excellent, it is therefore especially preferred that fuel cell applications.
＜ fuel cells ＞
Fuel cell is to take the power generator of electricity by being chemically reacted hydrogen and oxygen.In addition, fuel cell has admittedly Body high molecular fuel battery, phosphoric acid type fuel cell, fused carbonate type fuel cell, solid oxide fuel cell this 4 modes, wherein, polymer electrolyte fuel cell is since operating temperature is compared with low temperature (80 DEG C or so) and is high power generation effect Rate, therefore, is used for electronic equipment Miniature Power Unit, the emergency power supplies such as automobile using power source, home-use power generator, mobile phone etc. Purposes.
As shown in Figure 1, the battery 1 of representational polymer electrolyte fuel cell is that possess electrolyte film-electrode joint The structure of the separator 2 of 5 (MEA), the frame 6 of the above-mentioned MEA of support and the flow path formed with gas, above-mentioned electrolyte film-electrode There is conjugant 5 polyelectrolyte membrane 4 to be held in the structure between air electrode 3a, fuel electrode 3b.In addition, starting During polymer electrolyte fuel cell, fuel gas (hydrogen) and oxidizing gas (oxygen) pass through oxidizing gas flow passages 8a and fuel Gas flow path 8b is supplied.In addition, for the purpose for relaxing fever when generating electricity, cooling water flows through cooling water flow path 9.Should Illustrate, as shown in Fig. 2, overlapping hundreds of batteries and the device that is packaged are known as battery pack 10.
If supplying oxidizing gas (oxygen) to fuel electrode supply fuel gas (hydrogen), to oxygen electrode (air electrode), Reaction as described below then occurs in each electrode, the reaction (H of generation water occurs as a whole2+1/2O2→H2O).If in detail Illustrate, then as described below, in the proton (H of fuel electrode generation+) spread in solid polymer membrane and be moved to oxygen electrode side, Water (the H for reacting and generating with oxygen2O) discharged from oxygen electrode side.
Fuel electrode (anode electrode)：H2→2H++2e-
Oxygen electrode (cathode electrode)：1/2O2+2H++2e-→H2O
In order to start polymer electrolyte fuel cell, it is necessary to supply the fuel containing hydrogen to anode electrode with being individually insulated Gas, supply containing aerobic oxidizing gas cathode electrode.This is because if isolation is insufficient and gas and another gas Body mixes, it is likely that causes the decline of generating efficiency.According to such background, for preventing letting out for fuel gas, oxygen etc. The purpose of dew, mostly using sealant.Specifically, between adjacent separator, between separator and frame, frame Sealant is used between dielectric film or MEA etc..
Above-mentioned polyelectrolyte membrane can enumerate the cation-exchange membrane with ionic conductivity, from chemistry stablize, From the aspect of work under high temperature is strong, it can preferably enumerate with sulfonic fluorine system polymer etc..As commercially available product, can enumerate The Nafion (registration mark) of E.I.Du Pont Company, the Flemion (registration mark) of Asahi Kasei Corporation, Asahi Glass Co., Ltd Aciplex (registration mark) of system etc..Although, can be by using in general, the material of the difficult bonding of polyelectrolyte membrane The fuel cell of the present invention is bonded with photocurable.
Nafion (registration mark)
Above-mentioned fuel electrode is referred to as hydrogen electrode, anode, and known electrode can be used.For example, using making platinum, nickel, ruthenium etc. The electrode that catalyst loading is formed in carbon.In addition, above-mentioned air electrode is referred to as oxygen electrode, cathode, known electrode can be used. For example, use the electrode for making the catalyst loadings such as platinum, alloy be formed in carbon.The surface of each electrode, which can possess performance, expands gas Dissipate, make the gas diffusion layers of the effect of electrolyte moisturizing.Gas diffusion layers use known gas diffusion layers, such as can enumerate carbon Paper, carbon cloth, carbon fiber etc..
As shown in Figure 1, above-mentioned separator 2 has the thread road of convex-concave, fuel gas, oxygen are by the flow path, and supply is extremely Electrode.In addition, separator is made of aluminium, stainless steel, titanium, graphite, carbon etc..
Said frame is to be supported, strengthen in a manner of the dielectric film of film or MEA will not destroy.Said frame Material can enumerate polyvinyl chloride, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polypropylene (PP), the thermoplastic resin such as makrolon.In addition, in order to using the fuel cell photocurable of the present invention or it is solid Component is bonded by compound, preferred means printing opacity.As the adhering object of the present invention, these PEN and PP are particularly preferred.
The present invention fuel cell be with using the present invention fuel cell photocurable or its solidfied material into The fuel cell that row sealing is characterized.The component sealed as the needs in fuel cell, can enumerate separator, frame, electrolysis Matter, fuel electrode, air electrode, MEA etc..As more specifically sealing station, can enumerate between adjacent separator, every Between off member and frame, between frame and dielectric film or MEA etc..It should illustrate that " between separator and frame " or " macromolecule Between dielectric film or MEA and frame " the purpose of main sealing be to prevent the mixing of gas, leakage, adjacent isolation The purpose of sealing between part is the leakage for preventing gas and cooling water from cooling water flow path to External leakage.Should Illustrate, due to the atmosphere as the stronger acid compared with the acid generated from dielectric film, sealant requires acid resistance.
＜ encapsulating methods ＞
As the encapsulating method for the fuel cell photocurable for having used the present invention, it is not particularly limited, generation It can enumerate, FIPG (in-place molding gasket), CIPG (cured in place gasket), MIPG (on-site molding gasket), liquid note table Penetrate shaping etc..
FIPG is following method, i.e. using automatic coating device etc. to by the combustion of the flange coating present invention of containment member Expect battery photocurable, in the state of it is made with another lip fits, shone from the flange side for being transmissive to light Penetrate the method that ultraviolet isoreactivity energy-ray makes fuel cell carry out adhering and sealing with photo-curable sealant cures.More It is a kind of encapsulating method for body, it is characterised in that be that at least two by containment member with least two flange is convex The method that at least a portion between edge is sealed, at least one in above-mentioned flange are transmissive to active energy beam Light, above-mentioned encapsulating method include following process：At least one surface in above-mentioned flange is coated with above-mentioned fuel cell and uses up The process of curability sealant；A flange of above-mentioned Photocurable resin composition is coated with another flange via upper State the process that fuel cell is bonded with photocurable；And activity is irradiated by the above-mentioned flange for being transmissive to light Energy-ray makes above-mentioned fuel cell photo-curable sealant cures, by least a portion between above-mentioned at least two flange The process sealed.
CIPG is following method, i.e. using automatic coating device etc. to being applied combustion of the invention by the flange pearl of containment member Expect battery photocurable, irradiation ultraviolet isoreactivity energy-ray makes fuel cell photo-curable sealant cures And form gasket.Then, itself and another lip fits are made, the method for being compressed sealing.More specifically, it is a kind of sealing Method, it is characterised in that be by least one between at least two flange by containment member with least two flange Divide the method sealed, including following process：Above-mentioned fuel cell is coated with least one flange in above-mentioned flange to use up The process of curability sealant；The fuel cell photocurable of above-mentioned coating irradiation active energy beam is made above-mentioned Fuel cell photo-curable sealant cures, form the gasket work being made of the solidfied material of above-mentioned Photocurable resin composition Sequence；By the configuration of another flange on above-mentioned gasket, be coated with a flange of Photocurable resin composition with it is above-mentioned another One flange is crimped via above-mentioned gasket, the process that at least a portion between above-mentioned at least two flange is sealed.
MIPG is following method, i.e. mould is crimped on by the flange of containment member in advance, the material to being transmissive to light Mould and flange between produce chamber injection fuel cell photocurable, irradiation ultraviolet isoreactivity energy penetrate Line makes its photocuring, forms gasket.Then, the method for making it be compressed sealing with another lip fits.It should illustrate that Mould is preferably capable the material of transmitted light, specifically, can enumerate glass, polymethyl methacrylate (PMMA), poly- carbonic acid Ester, cyclic olefin polymer, alkene etc..In addition, in order to easily be taken out from mould being formed after gasket, mould is preferably pre-coated with fluorine The releasing agents such as system, silicon-type.More specifically, it is a kind of encapsulating method, it is characterised in that be by with least two flange At least two flange by containment member between the method that is sealed of at least a portion, including following process：Above-mentioned The process that gasket shape die for forming is configured at least one flange in flange；To above-mentioned gasket shape die for forming and it is configured with this The process that at least a portion in the gap between the flange of mould injects above-mentioned fuel cell photocurable；To above-mentioned Fuel cell photocurable, which irradiates above-mentioned active energy beam, makes above-mentioned fuel cell be consolidated with photocurable Change, the process for forming the gasket being made of above-mentioned fuel cell with the solidfied material of photocurable；By above-mentioned mould from upper State the process that a flange is removed；By the configuration of another flange on above-mentioned gasket, and by said one flange with it is above-mentioned another One flange is crimped via above-mentioned gasket, the process that at least a portion between above-mentioned at least two flange is sealed.
Liquid discharge shaping is following method, i.e. makes the fuel cell photo-curable of the present invention close by specified pressure Envelope agent flows into the mould for the material for being transmissive to light, and irradiation ultraviolet isoreactivity energy-ray makes its photocuring, forms gasket.So Afterwards, the method for making it be compressed sealing with another lip fits.It should illustrate that mould is preferably able to the material of transmitted light Matter, specifically, can enumerate glass, PMMA, makrolon, cyclic olefin polymer, alkene etc..In addition, in order to form gasket Easily taken out afterwards from mould, be preferably pre-coated with the releasing agents such as fluorine system, silicon-type in mould.
Embodiment
Hereinafter, enumerate embodiment to illustrate the present invention in more detail, but the present invention is not limited to these embodiments.
＜ (A) components ＞
The manufacture ＞ of ＜ a1 has the manufacture of the polyisobutylene polymer (a1) of acryloxy ethoxy phenyl
After carrying out nitrogen displacement in the container of the detachable flask of 5L, the n-hexane of 200mL and the fourth of 2000mL are added Base chlorine, is stirred while being cooled to -70 DEG C under blanket of nitrogen.Next, add the isobutene of 840mL (9mol), 12g The 2- picolines of the p-Diisopropylbenzene chloride and 1.1g (0.012mol) of (0.05mol).Reaction mixture is cooled to -70 After DEG C, the titanium tetrachloride for adding 5.0mL (0.05mol) starts to polymerize.After when polymerization beginning 3 is small, the acrylic acid of 40g with the addition of The titanium tetrachloride of phenoxy ethyl (LIGHT ESTER PO-A, Kyoeisha Chemical Co., Ltd.'s system) and 110ml.Then, -70 After when DEG C persistently stirring 4 is small, adding the methanol of 1000ml stops reaction.
Supernatant is separated from reaction solution, after evaporating solvent etc., product is dissolved in the n-hexane of 3000ml, 3 washings are carried out in the pure water of 3000ml, after carrying out reprecipitation from methanol, evaporate solvent under reduced pressure, the polymerization that will be obtained Thing is when 80 DEG C of vacuum drying 24 are small, so as to obtain the polyisobutylene polymer with acryloxy ethoxy phenyl (a1)。
Above-mentioned a1 includes-[CH2C(CH3)2]-unit, and contain 2 acryloyl groups.More specifically, a1 is in general formula (1) in, R1Represent phenylene, PIB represents polyisobutene skeleton, R4Represent the alkyl that carbon number is 2, R2And R3It is each independent Ground represents hydrogen atom, R5Represent hydrogen atom, n is 2 polyisobutylene polymer.
It should illustrate that the number-average molecular weight of a1 components (has used the polystyrene standard of size exclusion chromatography (SEC) to change Algorithm) it is that the viscosity of 11100, a1 components (using cone and plate viscometer measure in 25 DEG C of viscosity) is 1550Pas.
The preparation ＞ of ＜ fuel cell photocurables
Embodiment 1
As (A) component of the present invention, the polyisobutene with acryloxy ethoxy phenyl of 100 mass parts of addition Polymer (a1), the 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone as (B) component 3 mass parts of addition (IRGACURE1173, BASF society system), the methacrylic acid bicyclopentyl ester (FA- as (C) component 50 mass parts of addition 513M, Hitachi Chemical Co., Ltd.'s system), the 3- methacryloxypropyl trimethoxy silanes of 3 mass parts (KBM503, letter More Chemical Co., Ltd. system), under shading and room temperature, in planetary stirrer for mixing 60 minutes, so as to obtain as combustion Expect the embodiment 1 of battery photocurable.It should illustrate that embodiment 1 is liquid at 25 DEG C.
Embodiment 2
In embodiment 1, isobornyl methacrylate (SR-423, Sartomer society system) has been used to replace metering system Sour bicyclopentyl ester, in addition, is prepared by mode same as Example 1, so as to obtain embodiment 2.Should Illustrate, embodiment 2 is liquid at 25 DEG C.
Embodiment 3
In embodiment 1, stearyl methacrylate (SMA, Mitsubishi Gas Chemical Co., Ltd's system) has been used to replace Methacrylic acid bicyclopentyl ester, in addition, is prepared by mode same as Example 1, so as to be implemented Example 3.It should illustrate that embodiment 3 is liquid at 25 DEG C.
Embodiment 4
In embodiment 1, the methacrylic acid bicyclopentyl ester of 50 mass parts is set to 100 mass parts, in addition, led to Cross mode same as Example 1 to be prepared, so as to obtain embodiment 4.
Embodiment 5
In embodiment 1, the methacrylic acid bicyclopentyl ester of 50 mass parts is set to 20 mass parts, in addition, led to Cross mode same as Example 1 to be prepared, so as to obtain embodiment 4.
Comparative example 1
In embodiment 1, acrylic acid bicyclopentyl ester (FA-513AS, Hitachi Chemical Co., Ltd.'s system) has been used to replace first Base acrylic acid bicyclopentyl ester, in addition, is prepared by mode same as Example 1, so as to obtain comparative example 1。
Comparative example 2
In embodiment 1, isobornyl acrylate (IBX-A, Kyoeisha Chemical Co., Ltd.'s system) has been used to replace methyl Acrylic acid bicyclopentyl ester, in addition, is prepared by mode same as Example 1, so as to obtain comparative example 2.
The test method used in the embodiment of table 1, comparative example is as follows.
Fitness test ＞s of the ＜ to dielectric film
Various fuel cell photocurings are coated with a manner of as 50 μm of thickness on 400 μm of polypropylene (PP) film Property sealant, by the dielectric film (Dupont societies manufacture Nafion (registration mark)) with sulfonic fluorine system polymer with width Degree 10mm × length 2mm is bonded, and becomes 45kJ/m from the side of PP films with accumulative light quantity2Mode irradiate ultraviolet 20 seconds And it is set to cure and be used as test film.Then, using cupping machine, by fuel cell photo-curable on 180 degree direction The solidfied material of sealant was peeled off together with PP films from dielectric film with the speed of 10mm/ minutes.Based on following benchmark into Evaluation is gone.
[metewand]
Peel off adhesive strength：
◎ (excellent)：More than 0.2N/mm
Zero (good)：0.1N/mm is less than 0.2N/mm
× (poor)：Less than 0.1N/mm
Fitness test ＞s of the ＜ to PEN
Coating Examples 1 and the photo-curable of comparative example 1 are close in a manner of as 50 μm of thickness on 400 μm of PP films Agent is sealed, PEN is bonded with width 10mm × length 2mm, becomes 45kJ/m from the side of PP films with accumulative light quantity2Mode Irradiate ultraviolet 20 seconds and it is cured and is used as test film.Then, using cupping machine, by fuel on 180 degree direction Battery was peeled off from dielectric film with the solidfied material of photocurable together with PP films with the speed of 10mm/ minutes. Evaluated based on following benchmark.
[metewand]
Peel off adhesive strength：
◎ (excellent)：More than 0.2N/mm
Zero (good)：0.1N/mm is less than 0.2N/mm
× (poor)：Less than 0.1N/mm
【Table 1】
The present invention is rapid by the irradiation (20 seconds) of ultraviolet isoreactivity energy-ray according to the embodiment 1~5 of table 1 Ground cures, to the excellent adhesion of the dielectric film of the material as hardly possible bonding.In addition, to the close of PEN according to embodiment 1 Conjunction property is also excellent.
In addition, according to table 1, comparative example 1,2 is to have used acrylic acid bicyclopentyl ester, isobornyl acrylate to replace this hair Bright (C) component, but its result is to the bonding force difference of dielectric film.It is in addition, poor to the adaptation of PEN according to comparative example 1.
Comparative example 3
In embodiment 1, using urethane dimethacrylate (TE-2000, the Japanese Cao of polybutadiene skeleton Up to Co. Ltd. system) (A) component is replaced, in addition, prepared by mode same as Example 1, so as to obtain Comparative example 3.
Comparative example 4
In embodiment 1, using polyurethane diacrylate (UXF-4002, the Japanese chemical drug strain formula of polyether skeleton Commercial firm's system) (A) component is replaced, in addition, prepared by mode same as Example 1, so as to obtain comparative example 4。
＜ moisture permeabilitys (water vapor barrier property) ＞
The fuel cell that embodiment 1,2 and comparative example 3,4 have been flowed into the frame of 200mm × 200mm × 1.0mm is used up admittedly The property changed sealant.Then, 45kJ/m is become with accumulative light quantity with ultraviolet irradiation machine2Mode irradiate ultraviolet 20 seconds so that The solidfied material of the sheet of thickness 1.0mm is made.The calcium chloride (anhydrous) of 5g is added to the opening portion with diameter 30mm In aluminum cup, by the configuration of above-mentioned solidfied material in cup.After " gross weight at initial stage " (g) is determined, it is positioned over and maintains atmosphere In 40 DEG C of temperature and the constant temperature and humidity cabinet of relative humidity 95% 24 it is small when, measure " gross weight after placement " (g), calculate moisture permeability (g/m224h), evaluated based on following metewands.Show the result in table 2.Detailed test method is based on JIS Z 0208.It should illustrate that moisture permeability is as fuel cell sealant and in the case of use, 5g/m is preferably smaller than2· 24h。
[metewand]
○：Moisture permeability is less than 5g/m2·24h
△：Moisture permeability is 5g/m224h is less than 50g/m2·24h
×：Moisture permeability is 50g/m2More than 24h
＜ hydrogen barrier tests ＞
Using embodiment 1,2 and the fuel cell photocurable of comparative example 3,4, based on JIS K7126-1： 2006 (plastics-film and piece-permeability test methods-the 1：Differential pressure method) it is measured.It should illustrate that the species of experiment is pressure Power sensing method, condition be 23 DEG C, on high-tension side test gas (hydrogen) be 100kPa, thickness 1mm pieces be measured, be based on down Metewand is stated to be evaluated.Show the result in table 2.It should illustrate that hydrogen barrier is to be sealed using fuel cell In the case of agent, 1 × 10 is preferably less than-15mol·m/m2·s·Pa。
[metewand]
Zero (good)：Less than 1 × 10-15mol·m/m2·s·Pa
× (can not)：1×10-15mol·m/m2More than sPa
[changing 4]
Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 4
Moisture permeability ○ ○ Δ ×
Hydrogen barrier ○ ○ × ×
The present invention meets low moisture permeability needed for fuel cell sealant, hydrogen barrier according to the embodiment 1,2 of table 2 Property, there is good leakproofness.On the other hand, the carbamate dimethyl propylene of polybutadiene skeleton has been used in comparative example 3 Olefin(e) acid ester replaces (A) component, but its result hydrogen barrier is poor.In addition, the carbamic acid of polyether skeleton is used in comparative example 4 Ester diacrylate replaces (A) component, but its result moisture permeability, hydrogen barrier are poor.
Industrial utilizability
The fuel cell photocurable of the present invention is by the irradiation of ultraviolet isoreactivity energy-ray and rapid Ground cures, and the bonding force of dielectric film, PP, PEN to the material as hardly possible bonding is excellent therefore industrially useful.
Another mode of the present invention can be as follows.
〔21〕
A kind of fuel cell photocurable, it is characterised in that contain following (A)~(C) components.
(A) component：There is (methyl) acryloyl group of more than 1 in the molecule and include-[CH2C(CH3)2]-unit Polyisobutylene polymer,
(B) component：Optical free radical polymerization initiator,
(C) component：Methacrylate monomers.
〔22〕
According to the fuel cell photocurable described in above-mentioned (21), it is characterised in that above-mentioned (C) component is tool There are the methacrylate monomers of the alkyl of carbon number 5~30 or the methacrylate monomers with alicyclic structure.
〔23〕
According to the fuel cell photocurable described in above-mentioned (22), it is characterised in that the tool of above-mentioned (C) component The methacrylate monomers for having the alkyl of carbon number 5~30 are selected from metering system heptyl heptylate, methacrylic acid -2- ethyls Own ester, 2-Propenoic acid, 2-methyl-, octyl ester, isooctyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, methyl Isodecyl acrylate, lauryl methacrylate, methacrylic acid n-octadecane base ester, methacrylic acid isooctadecane base ester, More than a kind in methacrylic acid nonadecane base ester, 3- heptyl decyl -1- methacrylates, stearyl methacrylate,
The above-mentioned methacrylate monomers with alicyclic structure be selected from cyclohexyl methacrylate, methacrylic acid- 4- butylcyclohexyls ester, methacrylic acid bicyclopentyl ester, methacrylic acid dicyclopentenyl base ester, methacrylic acid dicyclopentenyl Epoxide ester, isobornyl methacrylate, adamantylmethacrylate, dicyclopentenyl dimethylacrylate, tricyclic More than a kind in decane dimethanol dimethylacrylate.
〔24〕
According to the fuel cell photocurable any one of above-mentioned (21)~(23), it is characterised in that The use level of above-mentioned (C) component is to contain 3~300 mass parts relative to above-mentioned (A) component of 100 mass parts.
〔25〕
According to the fuel cell photocurable any one of above-mentioned (21)~(24), it is characterised in that Above-mentioned (A) component is the polyisobutylene polymer represented by general formula (1).
(R1Represent monovalence or multivalence aromatic hydrocarbyl or monovalence or multivalence aliphatic alkyl.PIB is represented comprising-[CH2C (CH3)2The polyisobutene skeleton of]-unit.R4Represent the alkyl of the divalent that can include oxygen atom of carbon number 2~6.R2、R3 Each represent hydrogen atom, carbon number 1~20 1 valency alkyl.R5Represent hydrogen atom, methyl, ethyl or propyl group.N is 1~6 Any of.)
〔26〕
According to the fuel cell photocurable any one of above-mentioned (21)~(25), it is characterised in that As any structure in the separator of the component in fuel cell, frame, electrolyte, fuel electrode, air electrode, MEA The sealant on part periphery.
〔27〕
According to the fuel cell photocurable any one of above-mentioned (21)~(25), it is characterised in that As close between the sealant between the adjacent separator in fuel cell, separator and frame in fuel cell Envelope agent, fuel cell frame and dielectric film or MEA between sealant and use.
〔28〕
According to the fuel cell photocurable any one of above-mentioned (26), (27), it is characterised in that on It is polymer electrolyte fuel cell to state fuel cell.
〔29〕
A kind of fuel cell, it is characterised in that use up the fuel cell any one of above-mentioned (21)~(25) solid The property changed sealant is for the seal between the adjacent separator in fuel cell, separator and frame in fuel cell Any one in seal between the frame and dielectric film or MEA of seal, fuel cell between frame.
〔30〕
According to the fuel cell described in above-mentioned (29), it is characterised in that above-mentioned fuel cell is solid polymer type fuel Battery.
〔31〕
A kind of encapsulating method, it is characterised in that be to any in flange coating above-mentioned (21)~(25) by containment member Fuel cell photocurable described in, and in the state of making its lip fits with opposite side, from being transmissive to The flange side irradiation active energy beam of light, the sealing for making above-mentioned fuel cell be sealed with photo-curable sealant cures Method, by least one to be transmissive to light in the flange of the flange of containment member or opposite side.
〔32〕
A kind of encapsulating method, it is characterised in that be to any in flange coating above-mentioned (21)~(25) by containment member Fuel cell photocurable described in, irradiates active energy beam, makes above-mentioned fuel cell photo-curable close Envelope agent is solidified to form gasket, then, makes it with another lip fits and is compressed sealing.
〔33〕
A kind of encapsulating method, it is characterised in that mould is crimped at the flange by containment member in advance, to mould with it is convex The fuel cell photocurable any one of chamber injection above-mentioned (21)~(25) produced between edge, irradiation Above-mentioned active energy beam, makes its photocuring and forms gasket, then, it is sealed with another lip fits.
Symbol description
The battery of 1 polymer electrolyte fuel cell
2 separators
3a fuel-airs electrode (cathode)
3b air fuel electrodes (anode)
4 polyelectrolyte membranes
5 electrolyte film-electrode joints (MEA)
6 frames
7 bonding agents or sealant
8a oxidizing gas flow passages
8b fuel gas channels
9 cooling water flow paths
10 battery packs
11 polymer electrolyte fuel cells

Claims (14)

  1. A kind of 1. fuel cell photocurable, it is characterised in that containing following (A)~(C) components,
    (A) component：In the molecule with more than 1 it is (methyl) acryloyl group, with including-[CH2C(CH3)2]-unit The polyisobutylene polymer of polyisobutene skeleton,
    (B) component：Optical free radical polymerization initiator,
    (C) component：Methacrylate monomers.
  2. 2. fuel cell photocurable according to claim 1, wherein, (C) component is former with carbon The methacrylate monomers of the alkyl of subnumber 5~30 or with carbon number 5~30 ester ring type group methacrylic acid Ester monomer.
  3. 3. fuel cell photocurable according to claim 2, wherein, (C) component is former with carbon The methacrylate monomers of the alkyl of subnumber 5~30, the methacrylate monomers should with alkyl are selected from metering system Heptyl heptylate, methacrylic acid -2- ethylhexyls, 2-Propenoic acid, 2-methyl-, octyl ester, isooctyl methacrylate, decyl-octyl methacrylate, Lauryl methacrylate, isodecyl methacrylate, lauryl methacrylate, methacrylic acid n-octadecane base Ester, methacrylic acid isooctadecane base ester, methacrylic acid nonadecane base ester, 3- heptyl decyl -1- methacrylates, methyl More than a kind in stearyl acrylate base ester, alternatively,
    (C) component is the methacrylate monomers of the ester ring type group with carbon number 5~30, should have ester ring type The methacrylate monomers of group are selected from cyclohexyl methacrylate, methacrylic acid -4- butylcyclohexyls ester, metering system Sour bicyclopentyl ester, methacrylic acid dicyclopentenyl base ester, methacrylic acid dicyclopentenyl epoxide ester, the different ice of methacrylic acid Piece ester, adamantylmethacrylate, dicyclopentenyl dimethylacrylate, Tricyclodecane Dimethanol dimethacrylate More than a kind in ester.
  4. 4. according to fuel cell photocurable according to any one of claims 1 to 3, wherein, (C) component Use level be relative to (A) component described in 100 mass parts to contain 3~300 mass parts.
  5. 5. fuel cell photocurable according to any one of claims 1 to 4, wherein, (A) component For the polyisobutylene polymer represented by general formula (1),
    R1Represent monovalence or multivalence aromatic hydrocarbyl or monovalence or multivalence aliphatic alkyl, PIB is represented comprising-[CH2C (CH3)2The polyisobutene skeleton of]-unit, R4Represent the alkyl of the divalent that can include oxygen atom of carbon number 2~6, R2And R3Independently of one another represent hydrogen atom, carbon number 1~20 1 valency alkyl, R5Represent hydrogen atom, methyl, ethyl or third Base, n are any integer in 1~6.
  6. 6. according to fuel cell photocurable according to any one of claims 1 to 5, wherein, the fuel electricity Pond by the use of photocurable be the separator as the component in fuel cell, frame, electrolyte, fuel electrode, air electricity The sealant on the either member periphery in pole and electrolyte film-electrode joint.
  7. 7. according to fuel cell photocurable according to any one of claims 1 to 5, wherein, the fuel electricity Pond is the sealant between the adjacent separator in fuel cell, the isolation in fuel cell with photocurable It is close between the frame and dielectric film or electrolyte film-electrode joint of sealant or fuel cell between part and frame Seal agent.
  8. 8. the fuel cell photocurable according to claim 6 or 7, wherein, the fuel cell is solid High molecular fuel battery.
  9. 9. a kind of solidfied material, is that fuel cell according to any one of claims 1 to 5 is carried out light with photocurable Cure what is formed.
  10. 10. a kind of fuel cell, is comprising in the seal between the adjacent separator in fuel cell, fuel cell Separator and frame between seal and fuel cell frame and dielectric film or electrolyte film-electrode joint Between seal in the fuel cell of any one, any one described seal include claim 9 described in solidfied material.
  11. 11. fuel cell according to claim 10, wherein, the fuel cell is polymer electrolyte fuel cell.
  12. 12. a kind of encapsulating method, it is characterised in that be by least two flange by containment member with least two flange Between the method that is sealed of at least a portion, at least one light for being transmissive to active energy beam in the flange, The encapsulating method includes following process：Any one of at least one surface coating Claims 1 to 5 in the flange The process of the fuel cell photocurable；It is coated with a flange of the Photocurable resin composition The process being bonded with another flange via the fuel cell with photocurable；And it is transmissive to light by described Flange irradiation active energy beam make the fuel cell photo-curable sealant cures, by least two flange it Between the process that is sealed of at least a portion.
  13. 13. a kind of encapsulating method, it is characterised in that be by least two flange by containment member with least two flange Between the method that is sealed of at least a portion, including following process：At least one flange coating power in the flange The process that profit requires the fuel cell photocurable any one of 1~5；The fuel cell of the coating is used Photocurable irradiation active energy beam makes the fuel cell photo-curable sealant cures, is formed by the light The process for the gasket that the solidfied material of hardening resin composition is formed；By the configuration of another flange on the gasket, it will be coated with The flange and another described flange for having Photocurable resin composition are crimped via the gasket, by described at least The process that at least a portion between 2 flanges is sealed.
  14. 14. a kind of encapsulating method, it is characterised in that be by least two flange by containment member with least two flange Between the method that is sealed of at least a portion, including following process：Configured at least one flange in the flange The process of gasket shape die for forming；To the gap between the gasket shape die for forming and the flange for being configured with the mould at least The process that a part injects fuel cell photocurable according to any one of claims 1 to 5；To the fuel Battery photocurable, which irradiates the active energy beam, makes the fuel cell photo-curable sealant cures, shape Into the process for the gasket being made of the fuel cell with the solidfied material of photocurable；By the mould from one The process that flange is removed；By the configuration of another flange on the gasket, one flange and another described flange are situated between Crimped by the gasket, the process that at least a portion between at least two flange is sealed.
CN201680048479.3A 2015-08-18 2016-08-01 Photocurable sealing agent for fuel cell, and sealing method Active CN107925098B (en)

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